纳米碳材料非金属催化的研究进展

͵Ͷ ȋʹͲͳ͵Ȍ ͷͲͺȂͷʹ͵

ۢौᆜᣛ ʹͲͳ͵ᒪ ㅢ͵Ͷভ ㅢ͵ᵕ ȁ Ǥ Ǥ

a v a i l a

b l e a t w w w.s

c i e n c e

d i r

e c t.c o m

j o u r n a l h o m e p a g e : w w w.e l s e v i e r.c o m /l o c a t e /c h n j c

Review (Special Column on Progress in Catalysis in China during 1982Ͳ2012)

Research progress in metal Ǧfree carbon Ǧbased catalysts

ǡ ǡ ǡ ǡȗ

Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, Liaoning, China National Institute of Clean Ǧand ǦLow ǦCarbon Energy, Beijing 102211, China

Article history:

ͳͲ ʹͲͳʹ ͸ ʹͲͳ͵ ʹͲ ʹͲͳ͵

Ǧ Ǧ Ǥ ǡ ǡ ǡ Ǥ ǡ ǡ Ǥ Ǧ Ǧ ǡ ǡ Ǥ Ǧ Ǧ Ǧ Ǧ Ǥ

̹ ʹͲͳ͵ǡ ǡ Ǥ

Ǥ Ǥ Ǥ

Keywords: Ǧ

1. Introduction

Ǧ ǡ Ǥ Ǧ ǡ ǡ Ǧ ǡ ǡ ǡ Ǥǡ ǡ ǡ ǡ ȏͳԟ͵ȐǤ

Ǧ Ǧ ǡ Ǧ ǡ ǡ ǡ ȏͶǡͷȐǤ Ǧ Ǧ Ǧ

Ǥ ǡ Ǧ Ǥ Ǧ ǡ Ǧ ǡ ǡ Ǥ Ǧ ǡ Ǧ Ǧ Ǧ Ǥ

2. Structure and surface chemistry of nanocarbon materials

Ǥ ǡ ǡ ǡ ǡ

ȗ Ǥ ǣ Ϊͺ͸ǦʹͶǦͺ͵ͻ͹ͲͲʹͻǢ ǣ Ϊͺ͸ǦʹͶǦͺ͵ͻ͹ͲͲͳͻǢ Ǧ ǣ ̷ Ǥ Ǥ

ȋʹͳͳ͵͵ͲͳͲǡ ʹͳͳͲ͵ʹͲ͵ǡ ͷͲͻʹͳͲͲͶȌǡ ȋͻ͹͵ ǡ ʹͲͳͳ ͲͲͷͲͶȌǡ Ǥ

ǣ ͳͲǤͳͲͳ͸Ȁ ͳͺ͹ʹǦʹͲ͸͹ȋͳͳȌ͸ͲͷͳͷǦͻ ȁ ǣȀȀ Ǥ Ǥ Ȁ Ȁ Ȁͳͺ͹ʹʹͲ͸͹ ȁ Ǥ Ǥ Ǥǡ Ǥ ͵Ͷǡ Ǥ ͵ǡ ʹͲͳ͵

SUN Xiaoyan et al. / Chinese Journal of Catalysis 34 (2013) 508–523 ͷͲͻ

Ǥ

ǡ ǡ Ǥ Ǧ Ǥ Ǧ ǡ Ǧ Ǧ Ǥ Ǥ ͳ Ǧ ȏͶȐǤ Ǥ ǡ ǡ Ǥ ǡ Ǧ ǡ ǡ Ǥ

3. Catalytic performance of nanocarbon materials Ǧ Ǥ ǡ Ǧ Ȁ ǡ Ǧ Ǥ ǡ Ǧ Ǧ ǡ Ǧ ǡ Ǥ ǡ Ǥ ͳ Ǧ Ǧ ȏͷȐǤ 3.1. Gas phase reactions

ǡ Ǧ Ǥ ʹͲͲͳǡ Ú ǯ ȋ Ȍ Ǧ

ȏ͸ǡ͹Ȑ ͷͶ͹ ǡ Ǥ Ǧ ȋ Ǥ ʹȌǡ ȏͺԟͳ͵ȐǤ ǡ ȏͳͶȐǤ ʹͲͲͺǡ Ǥ ȏͳͷȐ Ƥ Ǥ ǡ ǡ Ǧ ͳͲͲԟʹͲͲ Ǧ Ǥ Ǧ Ǥ Ǧ Ǧ

O

N+

NH 2

O

O

O N+

N N N O O O

O OH

O O NH 2

O

O

OH

H O-Lactone

Carboxylic acid

Quinone

Ketone

Ether

Phenol Lactam

Pyrro le

Amide Amine Quaternary Carboxylic anhydride

Pyridine

oxide

Pyridine

Fig. 1. ȏͶȐǤ

Table 1

ǡ ȏͷȐǤ

Ȁ

Ȅ

x ȋ ͵ Ȍ ȋ Ȍ Ϊ

ȋ ͷǡ ͸Ȍ

ʹ ǡ Ȅ ͸

ʹ

20406080

100 Y i e l d (%)

CNT

CNF

Onion-like Carbon Fe-K-Ce -Mo-Mg Fe-K-Ce-Mg-Ca-Mo

Fig. 2.

ȏͳ͵ȐǤ

ͷͳͲ SUN Xiaoyan et al. / Chinese Journal of Catalysis 34 (2013) 508–523

ǡ Ǥ Ǧ Ǧ Ǧ α ǡ ǡ Ǧ Ǥ ǡ ȏͳ͸ȐǤ

Ǥ Ǥ ȏͳ͹Ȑ Ǧ Ȁ Ǥ Ǧ Ǧ ǡ Ǧ Ǥ ǯ ȏͳͺԟʹͲȐ Ǧ Ǧ Ǥ Ǧ ǡ Ǧ ǡ Ȁ ȏͳͻǡʹͲȐǤ Ǧ Ǧ ԟ Ǥ ǡ ǡ Ǥ ͵Ǥ Ǧ ǡ Ǧ ǡ ȏʹͳȐǡ ͳǦ ȏʹʹȐǡ ȏͳ͸Ȑǡ ȏʹ͵ȐǤ

Ǥ Ǥ ȏʹͶȐ Ǧ Ǥ ͵Ͳ ǡ ǡ ǡ ǡ ͸Ͳǡ ǡ Ǥ

Ǥ Ǧ ǡ ȏʹͷȐǤ Ǧ Ǥ Ǧ Ǥ ȏʹ͸Ȑ Ǥ ȏʹ͹ȐǤ Ǥ ȏʹͺȐ Ǧ ǡ ǡ Ǧ Ǧ Ǥ ǡ ǡ Ǧ Ǥ

Ǧ Ǧ Ǥ ȏʹͻȐ Ǧ Ǧ ȋ Ǥ ͶȌǤ ǡ Ǧ Ǥ Ǧ ǡ

R

R

H 2O

O 2

Fig. 3. Ǧ

Ǥ

204060

0.00.2

0.4

0.6

0.81.0

Y i e l d o r s e l e c t i v i t y

Time on stream (h)

Selectivity

Yield

(a)

Yield, nanodiamond

Selectivity, nanodiamond Yield, commercial catalyst

Selectivity, commercial

catalyst

Ether

Ketone

Carboxylic

acid

Hydroxyl

C (sp 3)C (sp 2)O H N

(b)

Fig. 4. ʹ ͵ Ǥ ǣ ͲǤͲͷ ǡͷͷͲ ǡ ʹǤͺΨ ǡ ͳͲ Ȁ ȏʹͻȐ ȋ Ȍ ȋ ȌǤ